Polymeric reaction products of unsaturated dilactones and complementary polyfunctional reactants



POLYMERIC REACTION PRODUCTS OF UNSATU- RATED DILACTONES AND COMPLEMENTARY POLYFUNCTIONAL REACTANTS Benjamin W. Howk, West Chester, Pa., and John C. Sauer,

Wilmington, Del., assignors to E. I. du Pont de'Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application November 25, 1955 Serial No. 549,153

15 Claims. (Cl. 26078.3)

This invention relates to new polymeric compositions and to their preparation. More particularly, this invention relates to new polymeric reaction products of certain unsaturated dilactones and complementary polyfunctional reactants.

New unsaturated dilactones are obtained when acetylenes are reacted with carbon monoxide in the presence of a catalytic amount of a cobalt carbonyl. These new unsaturated dilactones and their preparation are the subject matter of the copending patent application of J. C. Sauer, Ser. No. 432,599, filed May 26, 1954, now abandoned and continuation-in-part patent application thereof Ser. No. 549,155, filed Nov. 25, 1955. These new unsaturated dilactones correspond in composition to C (RR) O wherein R and R are hydrogen, haloaryl, alkoxyaryl, or hydrocarbon free from non-aromatic unsaturation, and show strong absorption lines in the ultraviolet spectra in the region of 3300-4400 A., and yield suberic acids on hydrogenation over platinum in acetic acid.

It is an object of this invention to provide new polymeric compositions and methods for their preparation. A further object is to provide new polymeric reaction products of certain unsaturated dilactones and complementary polyfunctional reactants. A still further object is to provide new polymers possessing thermosetting properties. Another object is to provide polymeric products which are useful in coating compositions and as components of printing inks. 7 Other objects will appear hereinafter. 1

These and other objects of this invention are accomplished by providing polymers of an unsaturated dilactone and a complementary polyfunctional reactant containing at least two groups which are reactive toward carboxyl, the unsaturated dilactone corresponding to C (RR) O wherein R and R are hydrogen, haloaryl, alkoxyaryl or hydrocarbon radicals free from nonaromatic unsaturation. It has been discovered that if these dilactones are reacted with a complementary poly-.

to the formula C (RR) O wherein Rand R' are.hy-'

drogen, alkoxyaryl, especially where the alkoxy radical is not more than 12 carbon atoms and the aryl radical is hydrocarbon of not more than 10 carbon atoms,.halo-' aryl, especially chloroaryl where the aryl radical is hydrocarbon of not more than 10 carbon atoms, or mono? valent hydrocarbon radicals free from non-aromatic unsaturation, especially of not more than 12 carbon atoms, e. g., alkyl, especially short chain alkyl, i. e., containing less than 7 carbon atoms, aryl, especially where the aryl radical is hydrocarbon of'riot more than 10 carbon atoms, aralkyl, especially of not more than 7 carbons, or cycloalkyl, particularly of not more than 7 carbon atomsr "Examples of such radicals are methyl,

v 2 ethyl, octyl, decyl, dodecyl, phenyl, tolyl, xylyl, benzyl,

cyclohexyl, naphthyl, methylcyclohexyl, methoxyphenyl. ethoxyphenyl, decyloxyphenyl, dodecyloxyphenyl, dodec-- yloxynaphthyl, chlorophenyl, chloronaphthyl, and them These dilactones show strong absorption lines in the ultraviolet spectra in the region of 3300-4400 A. and yield suberic acids on hydrogenation over platinum like.

in acetic acid.

These dilactones can be position isomers corresponding to the cis and trans forms of wherein R and R are defined as aforesaid. These unsaturated dilactones can be represented by the general 7:

wherein one free valence of each ring is satisfied by R "and the other free valences of said rings are satisfied by R, said Rand R being defined as aforesaid.

The dilactone from acetylene and carbon monoxide' is [A -bifuran]-5,5'-dione corresponding -,in formula to C H O and exists in two structural isomeric forms, a trans and a cis form, as follows:

HO=CH 0 (Lower melting isomer) Transform and *;C., respectively, when a setting is used such that the temperature increases from 175.-200.? C. in 6 minutes, from 200-225 C. in 9 minutes, and from 225-247 C. in 11 minutes. i V

The melting is generally accompanied-by sublimation and decomposition. The two isomers are further dis- Pafented June 24, 1958 tinguishedby their ultraviolet absorption: The lower melting isomer has its maximum absorption at about 3400 A., and its specificabsorbance, k is 200204.

The-higher melting; isomer has 1ts maximum absorption att about-13340 A and its specificabsorbance kg A, is-

220='224. Thus the ultraviolet specific absorbance for the C l-I compound'is from 200to 224. 1

On the basisof-the infrared spectra, thelower melting isomer is assigned the trans configuration and the higher t the low melting isomer,:is due to the bridge double bond.

In the trans structures; this double bond is astride a center of symmetry and will'riot absorbi The cis structure has no center of symmetry and the central double bond will absorb. The doublet at 6.5 in the spectra of the high melting form is due to the ethylenic double bond of each ring. The low melting form, shows only a single peak at 6.5;]. and this is consistent with a trans structure having a center of symmetry.

The complementary functional reactant is one which contains at least two groups which are reactive toward carboxyl, e. g., hydroxyl or amino containing at least one hydrogen attached to amino-nitrogen, i. e., primary or secondary amino groups. Preferred reactants are those which contain a plurality of amino or hydroxyl groups or both as the sole functional groups, particularly where theseamino and hydroxyl groups are separated by a hydrocarbonchain. These complementary reactants may be monomeric or polymeric and include. polyamines and polyhydroxy compounds. Examples of monomeric complementary reactants are ethylene, propylene, butylene, and octamethylene -glycols, diethylene glycol, glycerol, erythritol, and pentaerythritol, glycidol, sorbitol and mannitol, glycerol-a-monochlorohydrin, aminoethanol, 4 aminobutanol-l, ethylenediamine, hexamethylenediamine, octamethylenediamine, 1,4-diaminocyclohexane, bis(4- aminocyclohexane), bis(4 aminocyclohexyl)methane, piperazine, and the like. Polymeric complementary reactants include polyvinyl alcohol, reduced acrylonitrile polymersand copolymers, reductively aminated ethylene/ carbon monoxide copolymers, reduced nitrostyrene/butadiene copolymers, aminated glycidyl acrylat-e and methacrylatehpolymers and copolymers, reduced poly(3pentenenitrile), reduced poly(nitrostyrene), reduced nitrated butadiene/styrene copolymers, reductively aminated vinyl' ketone polymers and copolymers, andthe like.

In practice, the polymers of this invention are obtained by bringing into intimate contact the. dilactone and complementary reactant at a temperature within the range of 20 to 250 C. W

Another convenient wayfor preparing the polymers of this invention is by reacting the dilactone and complee. mentary reactant in a common inert organic solvent. When the reaction has proceeded to the desired stage, the solution can be used assuch'or the polymer may be separated from the solvent 'by drowning in a non-solvent, or by removing the solvent by distillation, preferably under reduced pressure. Still another way is by interfacial polymerization in which the reactants are each'dissolved in liquids which are mutually immiscible and the mixture is, then agitated atutemperatureswhich may be be low or abovenormalroom temperature until thedesired Example I L A glass tube was charged with 1.94 g. of piperazine.

to 17 hours.

prepared'as described subsequently. The tube was then evacuated to 1 mm. pressure'and sealed. The tube was heated at 190 C. for 6 hours, cooled, opened, and then heated at 200 C. in a vacuum: of l-2 mm. for 6 hours. The polymeric product was a friable brown solid, insolublein-xylene, dimethylformamide, methyl ethyl ketone, phenol-trichlorophenol mixture, etc.

The dilactone used in the above example was prepared as follows:

Intoa 400-ml. steelreactor was charged 26 g. of acetylene,200.ml."o acetone, and 1.5 g. of,dicobalt octacarbonyl. The mixture was heated at C. with carbon monoxide ata-pressure of 1000 atmospheres for 14 The product'was filtered and the brown solid was extracted with ethy acetate for 24 hours. The extract was permitted to crystallize and the crystalline material which .separatet was dried at room temperature. There was obtained 20 g. of a compound which by analysiscorresponds to C H O and whose structure is lA K i -bifuranl:5,5'-dione.

Example [I 'Fivetenths of agram of thedilactone of Example I' was mixed with 0.5 'g. of. tetraethylenepentamineat room temperature. Considerable heat was evolved. The product obtained was an, infusible polymer which was insoluble inhydrocarbons, ketones, esters, etc.

Examplelll Amixture of 0.49 g. of the dilactone of, Example I and 0.21. g. of diethanolamine to which one drop of tetraethylenepentamine had been added became a pasty.

polymeric solid at .room temperature. A small amount of carbon blaekwas added to this paste and the pigmented composition smeared over paper. The coating on the paper became tack-free when heated on a mandrel, at,

168 C. in a maximumof 5 seconds exposure time. When a commercial printing ink paste was used for a control under these conditions, it was still tacky.-

The advantagesof the above printing ink are two-fold:

(a) no solventis required,and (b) the ink is tack-free after a short baking period at a lower temperature than a typical commercial printing paste.

, Example IV An intirnate mixture of 1.64 g. of the dilactone of' Example I with 0.78 g. of pentaerythritol was heated in a Carver press under 1500 lb./ sq. in. pressure attcmperatures-varyingfrom to 200 C. A portion of the mixture whichhad been heated at 170C. in the Carver press was examined for thermosetting properties. This mixture-initially flowed between the platens of the press Example V A heavypaste was made by mixing together 2.46 g. of the dilactonej of Example I with 1.05 g. of diethanolamine- The-paste was placed in a Carver press and heated atw"; C. and 1500 lbL/sq. in. for IOminutes.

The; resulting 3 -mil thick sheet was homogeneous and t was unaffected by contact with such common organic solvents as, xylene, dimethylformamide, methylethyl ketone, dibutyl. sebacate, etc.

i Example Vl Example I and088 g. of polyvinyl alcohol there was added ml. of cyclohexanone and the mixture refluxed for one hour. The solution was then evacuated at 100 C. and 200-300 mm. pressure for 24 hours. The resulting polymeric product was not soluble in water and weighed 2.4 g.

Example 'VII 1 A paste made from 2.46 g. of the dilactone of Example I, 1.05 g. of diethanolamine and two drops of tetraethy1- enepentamine was pressed at 150 C. and 1500 lb./sq. in. pressure for 10 minute. The film was 3 mils thick and in a second heat treatment under the same conditions showed no flow.

A 3-mil film was made into a 4-ply film of 12 mils in thickness and .the composite heated at 150 C. in a Carver press. Although 3l-mil shims were used, this 4-ply film originally of12mils thickness dropped only to 9 mils and then stopped flowing entirely. i

A' portion of the paste prepared as above was heated in a Carverpress at 200 C. Under these conditions the film obtained showed no flow under pressure, indicating'that the polymer had thermoset. v

The product obtained by reacting the dilactone with diethanolamine in the presence of telraethylenepentamine analyzed as follows:

Analysis.-Calcd. for C H O :C H O N(C H O N) (i. e., 1 mole of dilactone+l mole of diethanolamine, ignoring the pentamine): C, 56.90%; H, 5.92%; H, 5.53%. Found: C, 57.11%; H, 5.73%; N, 5.78%.

Example VIII One gram of the dilactone of Example I and l g. of 1,1,4,4-tetramethyltetramethylenediamine were intimately mixed and the mixture was then diluted with a small amount of xylene. The mixture was heated at 50 to 60 C. to eifect solution, the heated solution was spread over a steel plate, and the plate was then baked for one hour at 100 C. The resulting coating of polyamide was hard and tack-free.

Example IX Molar equivalents of the dilactone of Example I and hexamethylenediamine were dissolved in dioxane at room temperature. An exothermic reaction ensued immediately and a solid material precipitated. The product obtained analyzed for the 1,1 adduct of the dilactone with hexamethylenediamine, plus one mole of water.

Analysis.-Calcd. for C H O N C, 56.36; H, 7.43; N, 9.39. Found: C, 57.86, 57.55; H, 7.78, 7.60; N, 9.37, 9.49.

Example X tained 14 g. of black polymeric material which was soluble in dilute ammonium hydroxide. The product analyzed as follows:

Analysis.Calcd. for c,,H,,N,o,: c, 60.43%; H,

6.5%; N, 10.08%; Found: C, 57.13%, 57.03%; H, 6.67%, 7.10%; N, 8.68%, 8.53%.

The dilactones used in preparing the polymers of this invention are the products disclosed and claimed in the copending patent application of J. C. Saue'r, U. 5. Ser.

No. 432,599,,filed May 26, 1954, now abandoned,- and continuation-impart patent application thereof Ser. No. 549,155 filed Nov. 25, formed by the reaction oftwo moles of an acetylene of, the formula R-CEC R' with four moles of carbon monoxide. The product from acetylene and carbon mon- V :organic solvent and a catalytic amount of a cobalt car-.

bonyl catalyst, the reactor is closed, cooled to 0 C., or lower, and evacuated. A predetermined amount of acetyleneis then admitted from a storage vessel calibrated so that the amount of acetylene delivered is measured by the 'drop in pressure, and the reactor placed in -a shaking device. Carbon monoxide is introduced to between 50 and 3000 atmospheres and the charge heated and agitated at 80 to 175 C. These conditions are maintained until there is no further reaction, as evidenced by cessation of pressuredropi Throughout the reaction period the pressure within the reactor is maintained within, the desired limits by periodic, injections of carbon monoxide. 1

After reaction is complete the reactor permittedf'toi,

' cool, unreacted acetylene and carbon monoxide are vented to the atmosphere, and the reactionmixture slurried with an inert organic solvent. residue on the filter extracted with a hot inert organic solvent. The extract is cooled and the crystalline product which separates is filtered and dried.

To 190 ml. of ethylene glycol there was added 8.2 grams of the dilactone of Example I in a flask fitted with a reflux condenser, gas inlet tube, and stirrer, and the mixture heated at reflux, with gaseous HCl being continuously bubbled through the refluxing mixture. After 6 hours at reflux the addition of HCl was stopped and approximately one half of the ethylene glycol removed by' The acetylenes used in preparing these dilactones cork respond to R- -CEC' -R, whereinR and R are hydrogen, alkoxyaryl, especially where the alkoxy radical is I not more than 12 carbon atoms and the aryl radical is hydrocarbon of not more than 10 carbon atoms, haloaryl, especially chloroaryl where the aryl radical is hydrocarbon of not more than 10 carbon atoms, or monovalent hydrocarbon radicals which are free from nonaromatic unsaturation, especially of not more than 12 carbon atoms, 6. g., alkyl, especially short chain alkyl, i. e., containing less than seven carbon atoms, aryl, especially where the aryl radical is hydrocarbon of not more than 10 carbon atoms, 'aralkyl, especially of not more than seven carbons, or cycloalkyl, particularly of not more than seven carbon atoms. Examples of such radicals are methyl, ethyl, octyl, decyl, dodecyl, phenyl, tolyl, xylyl,

reaction products, was continued for about 3 hours, during which time the pressure was gradually reduced to 0.7

mm. to maintain the temperature at 190 to 200 C. The polymer obtained was a rubbery solid, insoluble in solvent for the dilactone and ethylene glycol.

ExampleXI V Into a 250 ml. flask there were'added 8.2g. of the dilactone of Example I, 100 ml. of dioxane, and 5.7 g. of 2,5-dimethylpiperazine. The 'mixture'was heated to reflux with stirring for 1 hour. Thereafter the reaction mixture was allowed to cool to room temperature and the cold product separated by filtration. There wereob naphthyl, benzyl, cyclohexyl, methylcyclohexyl, chlorophenyl, chloronaphthyl, methoxyphenyl, ethoxyphenyl, decyloxyphenyl, dodecyloxyphenyl, dodecyloxynaphthyl, and the like. Examples of such acetylenes are acetylene, methyl acetylene, Z-decyne, phenylacetylene, naphthylacetylene, p-chlorophenylacetylene, p-ethoxyphenylacetylene, p-decyloxyphenylacetylene, benzylacetylene, cyclohexylacetylene, methylcyclohexylacetylene, etc.

By employing such substituted acetylenes in preparing the dilactones C (RR') O the radicals R and R' will correspond to the substituents attached to the triply bondedcarbon atoms in the'acetylene reactant, i. e., R' and R in R,CEC-RI.

Thus, as shown by said Sauer continuation-impart application, Serial No. 549,155, filed Nov. 25, 1955, there are prepared the dilactones:

1955. Chemically they are- The slurry is filtered and the V ofcarbo'n monoxide.

Thelreactionbetween theacetlene and carbon .monoxideiiscarried out batchwise or continuously in the presence {of an inert organic liquid medium. By inert organic liquid medium," asused herein, is meant organic liquids 'whichcontain no active hydrogen, as determined by the .Zerewitinoifjmettiod .[Ben 40, 2026 (1927); J. Am.'Chem. Soc. 49, 3181-(1 927)l. Thus, theacetylene is the only compoundinfthe reaction systemwhicl'rmay contain active hydrogen. Specifieinert organicliqu'ids are isooctane, toluene, aceton'itrile, acetone, ethyl acetate, dioxane, diethyl ether, xylene, benzene, etc. The nitriles and ketones are in general preferred over the hydrocarhens and ethers. p L

In'jthe formation of the dilactones, there are actually involvedl'rn'oles of an acetylene and 4 molesof carbon monoxide. In practice, this ratio is attained by charging a weighed sample of the acetylene into the reactor and then injecting carbon monoxide in amount sufficient to.

provide 2 moles thereof per mole off-acetylene. Employing a 400 ml. reactor and 25-30g. of acetylene, the amount. of carbon monoxide injected is that which will provide a total pressure in the range of 50-3000 atmospheresuat reaction temperature.

The reaction is conducted until there is no further pressure drop .and thisfgenerally requires from -20 hours, although shorter or longer reaction times can be employed. Throughout the reaction period the pressure within the reactor is maintained by periodic injections The-reaction between the dilactone and complementary polyfunctional reactant, occurs. at. ordinary atmospheric pressures. The use of pressures in some instances isdesirable either to reduce. the time of reaction or to. consolidate in one operation polymer formation'and"its conversion to a shaped object, e. g., a film.

"As illustr ated by the examples, the reaction between The time and temperature of the reaction depend upon:

the nature of the complementary reactant. As illustrated by' Example II with tetraethylenepentamine reaction occurs upon bringing the reactants together at ordinary room temperature. With less reactive reagents heattreatment is required. As a rule reaction occurs at temperatures which can range from ordinary room temperatureup to 250 C. Underthese temperature conditions, the time-.of.reaction can be, from a few minutes up to or more hours. i

In some instances an peratures under reduced pressure is desirableto remove last traces of unreacted reactants and low molecular weight products.

The complementary f reactant is generally used 'in amount which is at least equimola'r to the dilactone'f. If desired, however, one or the other may be used in excess.

When the complementary; reactant is& liquid, it may be I used in a large excess, in'whichevent it functions both as a reactant and reaction' medium: .Afteru'reaction is complete, the excess: may be removed by. distillation "or othermethods known to those skilled in the art.

and the like.

Asmany apparently'widely different embodiments of this invention may be madewithout departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows: 1. A polymeric reaction product .of an'unsaturated 'dilactone and an organic complementary polyfunctional reactant. containing at least two groups selected from the class consisting of hydroxyl and primary and secondary amino groups, said unsaturated dilactonehaving one of the formulas wherein one free valence of each ring in said formulas is satisfied by R and the other free valence of each ring in I said formulas is satisfiedby R, and R and R being selected from theclass consisting of hydrogen, alkoxyaryl where the alkoxy radical is not more than 12 carbon atoms and the aryl radical is hydrocarbon of not more than 10 carbon atoms, haloaryl where the aryl radical is hydrocarbon of not more than 10 carbon atoms, and

monovalent hydrocarbon radicals, free from non-aromatic unsaturatiom of not more than 12 carbon atoms.

2. A polymeric reaction product as set forth in claim .1 wherein said organic complementary polyfunctional reactant is an organic polyhydroxytcompound.

3. A polymeric reaction'product as set forth in claim 1 wherein said organic complementary polyfunctional reactant is a glycol. i l i 4. A polymeric reaction product as set forth in claim 1 wherein said organic complementary polyfunctional reactant is a polyamine wherein the amino nitrogens have at least one hydrogen attached thereto.

5. A polymeric reaction productas set forth in claim 1 wherein said organic complementary polyfunctional after-treatment at elevated tem- 1 9. A polymeric reaction product of lA fi- -bifuran]-5,5.-dione and ethylene alcohol.

.10.Apolyrnericreaction product of [A -bi furan] .-5,5'-dione and polyvinyl; alcohoL;

11. A polymeric reaction product of fA -hfl furan]-5,5'-dione and a polyamine wherein the amino nitrogens have at least one hydrogen attached thereto.

12. A polymeric reaction product of [A -bifuran]-5,5'-dione and a diamine wherein the amino nitrogens have at least one hydrogen attached thereto.

13. A polymeric reaction product of [A -bifuran]-5,5'-dione and piperazine.

14. A polymeric reaction product of [A -bifuran]-5,5'-dione and hexamethylene-diamine.

. 10 15. A polymeric reaction product of [A -bifuran]-5,5-dione and diethanolamine.

References Cited in the file of this patent (Copy in Sci. Library.) 

1. A POLYMERIC REACTION PRODUCT OF AN UNSATURATED DILACTONE AND AN ORGANIC COMPLEMENTARY POLYFUNCTIONAL REACTANT CONTAINING AT LEAST TWO GROUPS SELECTED FROM THE CLASS CONSISTING OF HYDROXYL AND PRIMARY AND SECONDARY AMINO GROUPS, SAID UNSATURATED DILACTONE HAVING ONE OF THE FORMULAS 